CN103524975B - A kind of halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material - Google Patents
A kind of halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material Download PDFInfo
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- CN103524975B CN103524975B CN201310516870.XA CN201310516870A CN103524975B CN 103524975 B CN103524975 B CN 103524975B CN 201310516870 A CN201310516870 A CN 201310516870A CN 103524975 B CN103524975 B CN 103524975B
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Abstract
The present invention relates to a kind of halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material, by unsaturated polyester resin, shrinking agent, cross-linking monomer, initiator, polymerization inhibitor, releasing agent, halogen-free flameproof composition and inorganic filler elder generation mix homogeneously, then compound is carried out with glass fibre, solidify under certain time and temperature after ripening, obtain halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material。The inventive method is simple, and the halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material prepared has good combination property, normality and excellent in mechanical performance under high temperature and halogen-free flameproof, meets environmental requirement。
Description
Technical field
The present invention relates to insulant field, especially relate to a kind of unsaturated polyester glass fibre composite material。
Background technology
Unsaturated polyester (UP) base glass fibre (chopped strand, chopped mat, continuous felt etc.) composite, there is electric property and the mechanical performance of excellence, unsaturated polyester (UP) has excellent hot-working type performance compared with epoxy resin, electrical property, production efficiency high, therefore the application of unsaturated polyester (UP) is increasingly extensive。
But the development along with automobile and electron trade, the demand of exotic material is also got more and more, but generally unsaturated polyester (UP) can only achieve the heatproof level of B level, the requirement of the high intensity of job demand under hot environment cannot be met, therefore, research and develop high temperature resistant type unsaturated polyester resin should be after major trend。
Additionally unsaturated polyester product is flame-retardant composition mostly is halogen, increase rapidly along with unsaturated polyester product is applied in industrial and agricultural production and daily life, the probability caught fire also is greatly increased, and the generation of fire can cause serious personal safety and property loss problem。Research finds, it is cause the main reason of casualties in fire that the toxic gas that material combustion produces makes personnel suffocate, and the material that content of halogen is more high, more easily produce toxic gas, therefore it is necessary for reducing the use that current halogen species is fire-retardant, the technical scheme adopting halogen-free flameproof substitutes, and meets the environmental requirement that current unsaturated polyester product is increasingly higher。
Summary of the invention
Technical problem solved by the invention is to provide that a kind of non-halogen is fire-retardant, have the normality mechanical performance of excellence and 150 DEG C of high temperature strength still show the halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material of excellence。
The purpose of the present invention is achieved by the following technical programs, a kind of halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material, count by weight, unsaturated polyester resin 70-85 part, shrinking agent 15-30 part, cross-linking monomer 5 parts, initiator 1-2 part, polymerization inhibitor 1.5-3 part, releasing agent 5 parts, halogen-free flameproof composition 5-20 part and inorganic filler 120-160 part, first by above-mentioned raw materials high-speed stirred mix homogeneously, then carry out compound with glass fibre 140-170 part, obtain gluing prepreg；Gluing prepreg is in drying room, and through ripening at low temperature at 40-50 DEG C, ripening was joined by thickness is folded after 24-72 hour, solidifies 2-10 minute, obtain halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material in die material at 130-140 DEG C of temperature。
The halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material of the present invention, wherein said unsaturated polyester resin is metaphenylene unsaturated polyester (UP), bisphenol type epoxy vinyl ester resin or epoxy novolac type vinyl ester resin。
The halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material of the present invention, wherein said shrinking agent is saturated polyester type shrinking agent, polystyrene type shrinking agent or polyvinyl acetate ester type shrinking agent。Saturated polyester type shrinking agent is preferably used polyethylene terephthalate type shrinking agent。
The halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material of the present invention, wherein said cross-linking monomer is styrene or α-methyl styrene。
The halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material of the present invention, wherein said initiator is cyclohexanone peroxide, methyl ethyl ketone peroxide, peroxidized t-butyl perbenzoate or tert-butyl hydroperoxide-2-ethyl acid ester。
The halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material of the present invention, wherein said polymerization inhibitor is hydroquinone, tert-butyl hydroquinone, methyl hydroquinone or 1,4-benzoquinone。
The halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material of the present invention, wherein said releasing agent is zinc stearate, calcium stearate or magnesium stearate。
The halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material of the present invention, wherein said halogen-free flameproof composition is phosphoric acid ester, APP, tripolycyanamide or melamine cyanurate。Described phosphoric acid ester is a class material such as triethyl phosphate, triphenyl phosphate, and this kind of material can use。
The halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material of the present invention, wherein said inorganic filler is aluminium hydroxide, calcium carbonate, silicon dioxide, aluminium sesquioxide, Kaolin, magnesium oxide or white carbon black。
The halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material of the present invention, wherein said glass fibre is long glass fibres, short glass fiber, glass cloth or glass felt。
Halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material provided by the present invention has the normality of excellence and hot mechanical performance, and the electrical property of excellence, temperature classification reaches F level, flame retardant rating is UL94V0, it is made both to have can apply to high-temperature insulation occasion, again can be effectively fire-retardant, it is ensured that life and property are from loss。
Detailed description of the invention
For further illustrating the present invention, illustrate with the following Examples:
The material used in following example is commercially available。
Embodiment 1
It is first according to weight fraction ratio epoxy novolac type vinyl ester resin 70 parts, polystyrene type shrinking agent 30 parts are put in agitator tank and stirred, and it is sequentially added into styrene 5 parts, tert-butyl hydroperoxide-2-ethyl acid ester 1.0 parts, 1,4-benzoquinone 1.5 parts, zinc stearate 5 parts, triethyl phosphate 20 parts when stirring, stir 5 minutes to mix homogeneously, add calcium carbonate 140 parts afterwards and improve speed of agitator, high speed dispersion 10 minutes, compound is carried out again with glass fibre 140 parts, then in drying room, through ripening at low temperature at 40 DEG C, ripening 72 hours。Ripening is complete joins by thickness is folded, solidifies 8 minutes, obtain halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material in die material at 130 DEG C of temperature。
Embodiment 2
It is first according to weight fraction ratio bisphenol type epoxy vinyl ester resin 80 parts, polyvinyl acetate ester type shrinking agent 20 parts are put in agitator tank and stirred, and it is sequentially added into styrene 5 parts, tert-butyl hydroperoxide-2-ethyl acid ester 1.5 parts, 1,4-benzoquinone 1.8 parts, zinc stearate 5 parts, tripolycyanamide 10 parts when stirring, stir 5 minutes to mix homogeneously, add calcium carbonate 120 parts afterwards and improve speed of agitator, high speed dispersion 10 minutes, compound is carried out again with glass fibre 140 parts, then in drying room, through ripening at low temperature at 40 DEG C, ripening 48 hours。Ripening is complete joins by thickness is folded, solidifies 8 minutes, obtain halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material in die material at 130 DEG C of temperature。
Embodiment 3
It is first according to weight fraction ratio metaphenylene unsaturated polyester (UP) 85 parts, polyethylene terephthalate type shrinking agent 15 parts are put in agitator tank and stirred, and it is sequentially added into styrene 5 parts, tert-butyl hydroperoxide-2-ethyl acid ester 2 parts, 1,4-benzoquinone 3 parts, zinc stearate 5 parts, triethyl phosphate 20 parts when stirring, stir 5 minutes to mix homogeneously, add calcium carbonate 160 parts afterwards and improve speed of agitator, high speed dispersion 10 minutes, compound is carried out again with glass fibre 140 parts, then in drying room, through ripening at low temperature at 40 DEG C, ripening 24 hours。Ripening is complete joins by thickness is folded, solidifies 5 minutes, obtain halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material in die material at 140 DEG C of temperature。
Embodiment 4
It is first according to weight fraction ratio epoxy novolac type vinyl ester resin 75 parts, polystyrene type shrinking agent 25 parts are put in agitator tank and stirred, and it is sequentially added into styrene 5 parts, tert-butyl hydroperoxide-2-ethyl acid ester 1.2 parts, 1,4-benzoquinone 1.5 parts, zinc stearate 5 parts, APP 10 parts when stirring, stir 5 minutes to mix homogeneously, add calcium carbonate 140 parts afterwards and improve speed of agitator, high speed dispersion 10 minutes, compound is carried out again with glass fibre 155 parts, then in drying room, through ripening at low temperature at 40 DEG C, ripening 48 hours。Ripening is complete joins by thickness is folded, solidifies 8 minutes, obtain halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material in die material at 130 DEG C of temperature。
Embodiment 5
It is first according to weight fraction ratio by epoxy novolac type vinyl ester resin 75 parts, polyvinyl acetate ester type shrinking agent 25 parts puts in agitator tank and stirs, and it is sequentially added into styrene 5 parts when stirring, tert-butyl hydroperoxide-2-ethyl acid ester 1.2 parts, 1,4-benzoquinone 1.5 parts, zinc stearate 5 parts, triethyl phosphate 5 parts, stir 5 minutes to mix homogeneously, add aluminium hydroxide 140 parts afterwards and improve speed of agitator, high speed dispersion 10 minutes, compound is carried out again with glass fibre 170 parts, then in drying room, through ripening at low temperature at 40 DEG C, ripening 48 hours。Ripening is complete joins by thickness is folded, solidifies 8 minutes, obtain halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material in die material at 130 DEG C of temperature。
Embodiment 6
It is first according to weight fraction ratio by epoxy novolac type vinyl ester resin 75 parts, polyvinyl acetate ester type shrinking agent 25 parts puts in agitator tank and stirs, and it is sequentially added into styrene 5 parts when stirring, tert-butyl hydroperoxide-2-ethyl acid ester 1.2 parts, 1,4-benzoquinone 1.5 parts, zinc stearate 5 parts, tripolycyanamide 15 parts, stir 5 minutes to mix homogeneously, add aluminium hydroxide 130 parts afterwards and improve speed of agitator, high speed dispersion 10 minutes, compound is carried out again with glass fibre 170 parts, then in drying room, through ripening at low temperature at 40 DEG C, ripening 48 hours。Ripening is complete joins by thickness is folded, solidifies 8 minutes, obtain halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material in die material at 130 DEG C of temperature。
Embodiment 7
It is first according to weight fraction ratio epoxy novolac type vinyl ester resin 75 parts, polyvinyl acetate ester type shrinking agent 25 parts are put in agitator tank and stirred, and it is sequentially added into styrene 5 parts, tert-butyl hydroperoxide-2-ethyl acid ester 1.5 parts, 1,4-benzoquinone 3.0 parts, zinc stearate 5 parts, APP 7 parts when stirring, stir 5 minutes to mix homogeneously, add aluminium hydroxide 140 parts afterwards and improve speed of agitator, high speed dispersion 10 minutes, compound is carried out again with glass fibre 170 parts, then in drying room, through ripening at low temperature at 40 DEG C, ripening 48 hours。Ripening is complete joins by thickness is folded, solidifies 8 minutes, obtain halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material in die material at 130 DEG C of temperature。
Embodiment 8
It is first according to weight fraction ratio by epoxy novolac type vinyl ester resin 75 parts, polyethylene terephthalate type shrinking agent 25 parts puts in agitator tank and stirs, and it is sequentially added into α-methyl styrene 5 parts when stirring, tert-butyl hydroperoxide-2-ethyl acid ester 1.2 parts, 1,4-benzoquinone 1.5 parts, zinc stearate 5 parts, APP 15 parts, stir 5 minutes to mix homogeneously, add calcium carbonate 160 parts afterwards and improve speed of agitator, high speed dispersion 10 minutes, compound is carried out again with glass fibre 170 parts, then in drying room, through ripening at low temperature at 40 DEG C, ripening 48 hours。Ripening is complete joins by thickness is folded, solidifies 8 minutes, obtain halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material in die material at 130 DEG C of temperature。
Measure the bending strength of composite material laminated board of gained, hot-state bending strength, the performance such as fire-retardant in Table 1。
Table 1
Embodiment described above is only that the preferred embodiment of the present invention is described; not the scope of the present invention is defined; under the premise designing spirit without departing from the present invention; various deformation that technical scheme is made by this area ordinary skill technical staff and improvement, all should fall in the protection domain that claims of the present invention are determined。
Claims (5)
1. a halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material, it is characterized in that: count by weight, unsaturated polyester resin 70-85 part, shrinking agent 15-30 part, cross-linking monomer 5 parts, initiator 1-2 part, polymerization inhibitor 1.5-3 part, releasing agent 5 parts, halogen-free flameproof composition 5-20 part and inorganic filler 120-160 part, first by above-mentioned raw materials high-speed stirred mix homogeneously, then carry out compound with glass fibre 140-170 part, obtain gluing prepreg；Gluing prepreg is in drying room, and through ripening at low temperature at 40-50 DEG C, ripening was joined by thickness is folded after 24-72 hour, solidifies 2-10 minute, obtain halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material in die material at 130-140 DEG C of temperature；
Described unsaturated polyester resin is bisphenol type epoxy vinyl ester resin or epoxy novolac type vinyl ester resin；
Described halogen-free flameproof composition is phosphoric acid ester, APP, tripolycyanamide or melamine cyanurate；
Described glass fibre is long glass fibres, short glass fiber, glass cloth or glass felt；
Described shrinking agent is saturated polyester type shrinking agent, polystyrene type shrinking agent or polyvinyl acetate ester type shrinking agent；
Described cross-linking monomer is styrene or α-methyl styrene。
2. halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material according to claim 1, it is characterised in that: described initiator is cyclohexanone peroxide, methyl ethyl ketone peroxide, peroxidized t-butyl perbenzoate or tert-butyl hydroperoxide-2-ethyl acid ester。
3. halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material according to claim 1, it is characterised in that: described polymerization inhibitor is hydroquinone, tert-butyl hydroquinone, methyl hydroquinone or 1,4-benzoquinone。
4. halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material according to claim 1, it is characterised in that: described releasing agent is zinc stearate, calcium stearate or magnesium stearate。
5. halogen-free flameproof height heat resisting unsaturated polyester glass fiber compound material according to claim 1, it is characterised in that: described inorganic filler is aluminium hydroxide, calcium carbonate, silicon dioxide, aluminium sesquioxide, Kaolin, magnesium oxide or white carbon black。
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| US20210139629A1 (en) * | 2018-04-12 | 2021-05-13 | Japan Composite Co., Ltd. | Unsaturated polyester resin composition, molding material, molded article, and battery pack housing for electric vehicles |
| WO2020080412A1 (en) * | 2018-10-19 | 2020-04-23 | ジャパンコンポジット株式会社 | Unsaturated polyester resin composition, molding material, molded article and battery pack case for electric vehicles |
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| CN111454557A (en) * | 2020-05-18 | 2020-07-28 | 江苏理工学院 | Preparation process of flame-retardant unsaturated polyester resin |
| CN111548602A (en) * | 2020-06-08 | 2020-08-18 | 常熟市华邦汽车复合材料有限公司 | Low-conductivity glass fiber reinforced molding compound |
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Effective date of registration: 20230425 Address after: 064300 Middle Zone of Qianxi County Economic Development Zone, Tangshan City, Hebei Province (Xingcheng Town, East Henan Zhai Village) Patentee after: Hebei Furunda New Materials Technology Co.,Ltd. Address before: 101111, Beijing Zhongguancun Haidian District science and Technology Park, Tongzhou Park light mechanical and electrical integration industrial base, light five street Patentee before: BEIJING FRIEND COMPOSITE MATERIALS CO.,LTD. Patentee before: BEIJING NEW FRIEND INSULATING MATERIAL Co.,Ltd. |